Compounds of the thiazolanthrone sulphone series and process of making same



Patented July 12, 1932 i ame? rAroFFicTE HEINRICH ITTER, orFRANKEORT-O1\T-'lI-IE-MAIl T-FECI-IENHEIM, nn ALFRED ROLL, FOFFENBACH-ON-THE-IVIAIN, GERMANY, AssIeNoRs re GENERAL ANILINE woRKs,

INC., or NEW YORK, N. Y, A CORPORATION or DELAWARE V v conrotmns on THETHIAZOLANTHBONE sULrEonE SERIES AND PROCE S or MAKING SAME p I 1 NoDrawing. Application filed November 4, 1930, Serial No. teases, and inGermanyNovember 8,1929.

Our invention relates to compounds of the thiazolanthrone sulphoneseriesand process of making same.

l/Ve have found that the sulphur atom of the meSo ring inthriazolanthrone and its nuclear substitution products can be oxidizedto the sulphone group by treatment with suitable oxidizing agents usualfor the conversion of organic sulphides into sulpho-ne compounds (cf.Houben, Methode der organischen Chemie, Vol. III (1930) page 127 8) ;inan acid medium. In this manner when starting from thiazolanthrone itselfthe thiazol-anthronesulphone of the probable formula V is obtained,which is identicalwith the anhydride of anthraquinone l-sulphamide,described by Ullman in Ber. der' deutschen Chem. Gesellschaft, vol. 52,page 550,

It appears from this fact, that by the present process of oxidationthering system of the starting material remains unchanged.

As suitable oxidizing agents, for example, hydrogen peroxide, halogens,permanganates, used in acid medium and chromic and fuming V nitric acidsmay be'mentioned.

The present oxidation products are valu-- able intermediates for theproduction of dyestuil's. So far as they .still contain one carbonylgroup they are distinguished by a remarkable solubility inalkalijsulphide solution and in the vat. V

So'far as they contain in 2 and 5 position further substituents such asa methyl or carboxylic acid group or halogen or in 5.10 position asecond thiazol-sulphone ring they are new compounds unknown hitherto.These new compounds correspond .to the probable general formula: V v

' of about 30% strength and the mixture is wherein X means hydrogen ormethylor carboxylic acid group, Y means hydrogen or halogen, one X or Ystanding forhydrogen,

parts being by weight and all temperatures in centigrade degrees. But wewish it to be understood that we are notlimited to the particularconditions norto the specific products mentioned therein. r V y -fExample 1 10 parts of thiazolanthrone are mixed with about 250 parts ofglacialacetic acid and 15 parts of a hydrogen peroxide, solution ofabout25 %strengthand the mixture is heated to boiling for a short time.From the originally clear solution-slowly a weakly yellowish precipitateseparates slowly, which is filtered off after heating for about twohours and washed out. It crystallizes from nitrobenzene in the form oflight yellow needles melt- The same compound is obtained when oxidizingwith chromic acid or when introducing an excess of chlorine into adilute solution of thiazolanthrone in glacial acetic acid. 05

p; Example? p I v 7 5 parts of 2-methylthiazolanthrone are mixed withabout 300 parts of glacial acid and 10 parts of a hydrogen peroxidesolution heated to boilingfor about two hours. When i 7 cool theprecipitate is filtered off. The new oxidation product corresponding tothe probable formula:

crystallizes from, for instance, monochloro benzene in the form ofyellow crystals melting at about 27 0 with decomposition. The VQ-methyIthiaZo-la-nthrone-sulph'one "dissolves azolanthrone.

tacked.

J Example 3 i I 5 parts of thiazolanthrone-Qcarboxylic time.

crystals are filtered off and washed out; The

acid are mixed with aboutQOO parts of glacial acetic acid and 6 partsofchromic acid and the mixture is heated to boiling for a short Whencoolthe precipitated yellow new oxidation product represents thethiazolanthrone-sulphone-2-carboxylic acid of the probable formula: IN-so3 It maybe purified by recrystallization from,

for instance, nitrobenzene or glacial acetic acid] It is then obtainedin the form of yellow needles, which are nearly colorless, soluble indilute alkali solutions and vattable with a bluish green color. I

Instead ofchromic facid likewise .ahydrogen peroxide solution may beused.

Ewamplet Into a solution of 5 parts of 5-chlorothiazolanthrone in-about100125, parts of dilute acetic acid, which has been warmed at about5O6(), a weak current ofchlorine is introduced. After allowing thereaction mass to stand for some time by adding water thereto the formednew oxidation productv is separated. It represents the5-chlorothiazolanthronesulphone of theiprobable formula: V

peroxide solution. 7 r v V 3. As new-products compounds of thethirecrystallizing from, for instance, nitrobenzene in the form ofbeautiful yellow crystals melting above 800.

Example 5 5 parts of 1.5-dithiazolanthrone are mixed with about 200parts of glacial acetic acid and 12 parts of a hydrogen peroxidesolution of.

about 30% strength and the mixture is heated to boiling for about anhour. Then the separated orange crystals are filtered ofi, washed outand advantageously recrystallized from, for instance, nitrobenzene, fromwhich orange crystals separate which melt above 300. The newdithiazolanthronesulphone I of the probable formula:

TIL-SO O I dOz-bl thus obtained is soluble sulphuric acid with a yellowcolor, but not showing fluorescence whereas the solution of the startingmaterial in sulphuric acidis characterized by a strong greenfluorescence.

We claim:

1. A process for producing oxidation products which process comprisestreating compounds of the thiazolanthrone series with an oxidant usualfor the conversion of organic 1 sulphldes lnto sulphone compounds in anacid medium. V

2. A process for producing oxidation products which processcomprisestreating {compounds of they thiazolanthrone series dissolved in glacialacetic acid with a hydrogen azolanth'rone sulphone series correspondingprobably to the general formula:

wherein X means hydrogen or a methyl ora carhoxylic acid group,'Y meanshydrogen or halogen,one X or Y standing for hydrogen,

' l a ll Z means oxygen or'Y andZ jointly SO N, which products areyellowish colored crystalline substances.

4. As new 'products compounds of the thiazolanthrone" sulphone seriescorresponding probably to the general'formula g bIslozl g Vazola-nthrone-sulphone of the probable formula forming yellow crystalsmelting at about 270 with decomposition, being soluble in concentratedsulphuric acid with a yellow color and being vattable with a violet-redcolor.

6. As a new compound the thiazolanthronesuphone-Q-carboxylic acid of theprobable formula:

v V III-S02 COOH forming yellow needles, nearly colorless soluble indilute alkali solutions and vattable with a bluish green color.

7. As a new compound the 5-chlorothiaz'olanthrone-sulphone of theprobable for,- Inula:

' N-SO:

QQ/O

forming beautiful yellow crystals melting above 300.

In testimony whereof, we afiix our signatures.

HEINRICH BITTER. ALFRED HOLL.

